Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/08—Butenes
  • C08F110/10—Isobutene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/08—Butenes
  • C08F10/10—Isobutene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/02—Carriers therefor
  • C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
  • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
  • C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
  • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
  • C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene

Definitions

• the invention is directed to an improved process for the preparation of polybutene having an exo-olefin content of at least 50 mol. % by the polymerization of iso-butene, or a C 4 feed comprising iso-butene and other C 4 olefins using (i) a Lewis acid•Lewis base catalyst complex and an alkyl halide initiator capable of initiating cationic polymerization, in a substantially or completely apolar polymerization medium, where the catalyst complex is pre-activated with water.
• Dispersants based on polybutene succinimides are ubiquitous in lubricating oils worldwide.
• An essential step in the manufacture of these dispersants is maleation of polybutene to polybutene succinic anhydride, which is further aminated with a polyamine to produce the succinimide.
• the maleation process is facilitated by polyisobutylene (PIB) with a high level of vinylidene at the polymer terminus, which can react smoothly with maleic anhydride in a thermal or "ene", without the need for chlorine as a facilitator.
• PIB polyisobutylene
• HR-PIB highly reactive PIB
• the Lewis acid ionizes the initiator to start polymerization, and the Lewis base deprotonates the polymeric carbenium to the desired olefin.
• the binding strength of the LA•LB complex is dependent on the nature of LA and LB as well as on the environment.
• a Lewis acid•Lewis base complex of EtAlCl 2 (EADC) and di-isopropyl ether is able to produce HR-PIB with high vinylidene levels.
• a high concentration of CEE can decrease the rate of IB polymerization because it inhibits dissociation of the LA•CEE complex which dissociation is required to ionize the t-BuCl initiator. Long residence times and large reactors would then be required to realize commercially reasonable monomer conversions.
• the high rate of deprotonation also lowers the molecular weight (MW) of the polymer product because it interrupts chain growth. Therefore, a means to simultaneously achieve high terminal vinylidene, high monomer conversion and high MW simultaneously using aluminum based catalysts at reasonable temperatures would be very valuable to the industry.
• USPN 7,411,104 teaches the addition of tertiary alcohols such as t-butanol in combination with a secondary alkyl ether, such as di-isopropyl ether, during the polymerization of IB using a BF 3 catalyst to enhance the vinylidene content of the resulting HR-PIB polymer.
• a secondary alkyl ether such as di-isopropyl ether
• USPN 10, 174, 138 teaches that, in a polymerization process for the preparation of polybutene by polymerization of iso-butene, or a C 4 feed comprising iso-butene and other C 4 olefins using AlCl 3 or alkyl AlCl 2 Lewis acids (LA) complexed with ether Lewis bases having an electron-withdrawing group (LB) as the catalyst and an alkyl halide initiator, in a substantially or completely apolar polymerization medium, the presence of a tertiary alcohol, when used in relatively small amounts, will increase the terminal vinylidene content of the resulting polybutene product without causing a corresponding reduction in molecular weight.
• LA alkyl AlCl 2 Lewis acids
• LB electron-withdrawing group
• USPN 10,047,174 and USPN 10,167,352 teach that, in a polymerization process for the preparation of polybutene by polymerization of iso-butene, or a C 4 feed comprising iso-butene and other C 4 olefins using AlCl 3 or alkyl AlCl 2 Lewis acids (LA) complexed with ether Lewis bases having an electron-withdrawing group (LB) as the catalyst and an alkyl halide initiator, in a substantially or completely apolar polymerization medium (and in both the presence and absence of oxygenate impurities in the monomer feed), the pre-activation of the catalyst with small amounts of water allows for steady state and high yields of HR-PIB, particularly when using a continuous reaction, such as a continuous reaction performed using a continuous stirred tank reactor (CSTR).
• CSTR continuous stirred tank reactor
• HR-PIB derived from a continuous process using catalyst pre-activated with water tended to have a relatively high polydispersity index (PDI) of about 3 or above, which is substantially higher than the PDI of commercially available HR-PIB produced via cationic polymerization of isobutylene (IB) utilizing BF 3 catalyst. It was found that the PDI value was not significantly improved by increased mixing during the reaction or by modifying the reaction temperature or pressure, which indicates that the elevated PDI was related to the specific catalyst system chemistry.
• PDI polydispersity index
• An increase in the PDI of HR-PIB used to form dispersants may result in an increase in the viscosity of additive packages and lubricants formulated with such dispersants, which is a great disadvantage, particularly in an industry in which the trend is leading to lower viscosity lubricating oil compositions providing improved fuel economy performance.
• a method for the control of HR-PIB PDI using mixed ethers together with ethyl aluminum dichloride (EADC) was previously reported ( Kostjuk et al., Polymer 99, 2015, 633-641 ). However, the lowest PDI obtained via that method was 2.4, which remains above the industry standard value of 1.8 to 2.2.
• Lewis acids useful in the practice of the present invention include Lewis acids of the formula R'AlCl 2 , wherein R' is a hydrocarbyl group, preferably a hydrocarbyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 12 carbons.
• R' is a hydrocarbyl group, preferably a hydrocarbyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 12 carbons.
• hydrocarbyl means a chemical group of a compound that contains hydrogen and carbon atoms and that are bonded to the remainder of the compound directly via a carbon atom. The group may contain one or more atoms other than carbon and hydrogen (“hetero atoms”), provided such hetero atoms do not affect the essentially hydrocarbyl nature of the group.
• Useful Lewis bases are dihydrocarbyl ethers wherein each hydrocarbyl group is independently selected from hydrocarbyl groups having 1 to 8 carbon atoms.
• the hydrocarbyl groups of the ether may be branched, straight-chained or cyclic. Where the hydrocarbyl groups of the ether are branched or straight-chained, the hydrocarbyl groups are preferably alkyl groups, more preferably alkyl groups having 1 to 4 carbon atoms.
• One or both hydrocarbyl groups of the dihydrocarbyl ether are substituted with an electron withdrawing group, particularly a halogen atom, preferably a chlorine atom.
• the Lewis acid and Lewis base can be complexed by, for example, by dissolving the Lewis acid in a solvent selected from liquid, apolar, non-halogenated aliphatics, and liquid aromatics, such as benzene, chlorobenzene, toluene and xylene, to form a solution and then adding the Lewis base to the solution, while the solution is stirred.
• a solvent selected from liquid, apolar, non-halogenated aliphatics, and liquid aromatics, such as benzene, chlorobenzene, toluene and xylene
• the solvent is a non-halogenated aliphatic or aromatic solvent, and is more preferably xylene or toluene or mixed C 4 to C 12 linear and/or branched hydrocarbons (e.g., ISOPARTM, available from ExxonMobil Corporation), most preferably toluene or mixed C 4 to C 12 linear and/or branched hydrocarbons.
• xylene or toluene or mixed C 4 to C 12 linear and/or branched hydrocarbons
• the molar ratio of Lewis acid to Lewis base in the complex will typically be maintained within a range of from about 1:1 to about 1:8, preferably from about 1:1 to about 1:8, more preferably from about 1:1 to about 1:6, such as about 1:1 to about 1:3 (e.g. about 1:1.5).
• water may be added to the Lewis acid•Lewis base complex, which is then allowed to age for a period of time before being brought into contact with the feedstock.
• Water may be added to the Lewis acid/Lewis base complex in an amount of from about 0.02 to about 10 equivalents of water per equivalent of Lewis acid, preferably from about 0.03 to about 0.2 (such as from about 0.05 to about 0.15) equivalents of water per equivalent of Lewis acid.
• the activating water may be introduced to the Lewis acid•Lewis base complex via a saturated solution in toluene, which may be done at room temperature. Alternatively, the water may be introduced directly, if dissolved in the Lewis base.
• the Lewis acid•Lewis base complex is preferably allowed to sit for a period of time before use in order to allow the water to pre-activate the complex. Activation times may be from 1 minute to one day, preferably from about 2 minutes to about 3 hours, such as from about 5 minutes to about 60 minutes. Preferably, during activation, the complex can be maintained at a temperature of from about -10°C to about 20°C.
• the water treated, pre-activated catalyst complex is then reacted with from about 0.1 to about 2, preferably from about 0.2 to about 1.5, more preferably from about 0.3 to about 1.0 molar equivalents of a trialkyl aluminum (R" 3 Al, wherein R" is an alkyl group having 2 or more carbon atoms) per equivalent of Lewis acid.
• Suitable trialkyl aluminums include, for example, trioctyl aluminum, triisobutyl aluminum and triethyl aluminum.
• an “initiator” is defined as a compound that can initiate polymerization, in the presence or absence of adventitious water and in the presence of a proton trap.
• the initiator of the present invention (RX) comprises a hydrocarbyl R group, preferably an alkyl or aryl-alkyl group, wherein the carbon linking group R to X is tertiary, benzylic or allylic, preferably tertiary, which hydrocarbyl group can form a stable carbocation (e.g., t-butyl + ); and an X group, which is a halide, preferably chlorine.
• the polymerization medium must be a substantially or completely apolar polymerization medium, such as a mixture of saturated and unsaturated C 4 hydrocarbons.
• the feedstock may be pure isobutylene or a mixed C 4 hydrocarbyl feedstock containing isobutylene, such as a C 4 cut resulting from the thermal or catalytic cracking operation of, for example, naphtha.
• suitable feedstocks will typically contain at least 10%, and up to 100% isobutylene, by mass (e.g. 20-50%, based on the total mass of the feed).
• feedstocks containing isobutylene may also contain other non-C 4 polymerizable olefin monomers in minor amounts, e.g., typically less than 10%, preferably less than about 5%, and most preferably less than 1%, such as propadiene, propylene and C 5 olefins.
• the feedstock may contain various polar feed impurities such as acetone, methanol, acetonitrile, propionic acid, but will preferably be purified so that the feedstock contains less than 5 ppm, such as less than 4 ppm or 3 ppm or 2 ppm or 1 ppm or 0.5 ppm of polar impurities.
• polybutene as employed herein is intended to include not only homopolymers of isobutylene, but also copolymers of isobutylene and one or more other C 4 polymerizable monomers of conventional C 4 cuts as well as non-C 4 ethylenically unsaturated olefin monomers containing 5 carbon atoms, provided such copolymers contain typically at least 50 mass %, preferably at least 65 mass %, and most preferably at least 80 mass% isobutylene units, based on the polymer number average molecular weight ( M n ).
• the amount of the Lewis acid•Lewis base complex employed in the process of the present invention can be controlled, in conjunction with the concentration of initiator and monomer, reaction time and temperature, to achieve the target M n of the polybutene polymer product, the conversion of iso-butene and yield of polybutene.
• the Lewis acid•Lewis base complex is typically employed in an amount sufficient to contact the butene monomer in a liquid phase reaction mixture at a concentration of millimoles of Lewis acid•Lewis base complex per liter of reaction mixture of from about 0.2 mM to about 200 mM, such as from about 1 mM to about 200 mM, preferably from about 5 mM to about 100 mM, and more preferably from about 10 mM to about 50 mM, such as about 10 mM to about 30 mM.
• the initiator will typically be employed in a liquid phase reaction mixture comprising the iso-butene monomer at a concentration of millimoles of initiator per liter of medium, and independent from the amount of Lewis acid•Lewis base complex, of from about ImM to about 500 mM, preferably from about 2 mM to about 300 mM, and more preferably from about 2 mM to about 200 mM, such as about 10 mM to about 30 mM.
• the polymerization reaction can be performed as a batch or continuous process. On an industrial scale, the polymerization reaction is preferably conducted continuously.
• the continuous process can be carried out in tubular reactors, tube-bundle reactors or loop reactors, or tube or tube-bundle reactors with continuous circulation of the reaction material, or in a stirred tank reactor (glass, carbon steel or Monel preferred), a pump around loop, a plugged flow reactor or a combination thereof.
• the polymerization reaction is conducted in the liquid phase to induce linear or chain-type polymerization, as opposed to ring or branch formation.
• a feed that is gaseous under ambient temperature
• Typical C 4 cuts comprising the feed are liquid under pressure and do not require a solvent or diluent.
• Typical diluents suitable for use with the process include C 3 to C 6 alkanes, such as propane, butane, pentane and isobutane.
• the Lewis acid•Lewis base complex is typically introduced into the reactor as a liquid partially or completely dissolved in a solvent, or as a solid. Polymerization is preferably conducted at a pressure sufficient to maintain the C 4 feed in a liquid state at the reaction temperature, or at higher pressures.
• the initiator may be introduced to the monomer feed or the reaction mixture in liquid form together with the Lewis acid-Lewis base complex or, preferably, is introduced to the monomer feed or the reaction mixture in liquid form by a line separate from the Lewis acid-Lewis base complex addition line.
• the liquid phase reaction mixture temperature is controlled by conventional means to be typically from about -30°C to about +50°C, preferably from about -10°C to about +30°C, more preferably from about -5°C to about +20°C, such as about 0°C to about +15°C to minimize refrigeration costs and unwanted side reactions.
• turbulent flow of the reactor contents can be generated by mixing, or with suitable baffles, such as baffle plates or oscillating baffles, or by dimensioning the reactor tube cross sections so that a suitable flow velocity is established.
• the steady state residence time of the butene to be polymerized may be from about 1 to about 300 minutes, such as 2 to about 120 minutes, preferably from about 4 to about 60 minutes or from about 5 to about 45 minutes (e.g., from about 6 to about 30 minutes).
• the process of the present invention is typically conducted in a manner achieving an isobutylene conversion in the range of from about 20% up to about 100%, preferably from about 50% to about 100%, and more preferably from about 70% to about 100%, such as 80% to 100%, 90% to 100% or 95% to 100%.
• the combined use of temperature control and catalyst feed rate permits formation of polybutenes having a M n of from about 400 Daltons to about 4000 Daltons, preferably from about 700 Daltons to about 3000 Daltons, more preferably from about 1000 Daltons to about 2500 Daltons; a molecular weight distribution (MWD) of typically from about 1.1 to about 4.0, preferably from about 1.5 to about 3.0, an exo-olefin content of greater than 50 mol.
• MWD molecular weight distribution
• % preferably greater than 60 mol. %, more preferably greater than 70 mol. %, such as from about 80 mol.% to about 95 mol. %; a tetra-substituted olefin content of less than about 20 mol. %, such as less than about 15 mol. %, preferably less than about 10 mol. %, more preferably less than about 5 mol. %; and a chlorine content of less than about 10 mol. %, such as less than about 5 mol. %, preferably less than about 2 mol. %, more preferably less than about 1 mol. % based on the total moles of polymer.
• the polymer product can be discharged from the reactor and passed into a medium that deactivates the polymerization catalyst and terminates the polymerization.
• Suitable deactivation media include water, amines, alcohols and caustics.
• the polyisobutylene product can then be separated by distilling off the remaining C 4 hydrocarbons and low molecular weight oligomers. Preferably residual amounts of catalyst are removed, usually by washing with water or caustic.
• the Lewis acid is R'AlCl 2 , wherein R' is C 1 to C 4 hydrocarbyl, specifically, MeAlCl 2 , EtAlCl 2 (EADC), iso-BuAlCl 2 or n-BuAlCl 2 , the Lewis base is a chlorinated dihydrocarbyl ether (CEE), the solvent is ISOPAR or toluene, and the complex is formed by dissolving the Lewis base, or the Lewis base and water in the solvent to form a solution and then adding the Lewis acid to the Lewis base solution in an amount such that the molar ratio of Lewis acid to Lewis base in the complex is from about 1:1 to about 1:1.5.
• R' is C 1 to C 4 hydrocarbyl, specifically, MeAlCl 2 , EtAlCl 2 (EADC), iso-BuAlCl 2 or n-BuAlCl 2
• the Lewis base is a chlorinated dihydrocarbyl ether (CEE)
• the solvent is ISOPAR
• Ethyl aluminum dichloride (EADC) • chlorinated dihydrocarbyl ether (CEE) complex was prepared in a N 2 atmosphere glove box. An appropriate amount of EADC in hexane (1M) was mixed with CEE in a 1:2 molar ratio. Toluene containing 0.075 equivalents of H 2 O relative to EADC was added to the complex to form a 0.1M complex solution.
• the catalyst solution was delivered to the CSTR via a SS syringe pump.
• the initiator was delivered as a tBuCl solution in hexane via another SS Syringe pump.
• the feed, synthetic Raffinate-1 containing 40% IB was passed through a 3A and AZ300 column before introduction into the CSTR.
• the Raffinate-1 feed had less than 0.5 ppm polar (oxygenate) impurities, as determined by ASTM D7423.
• Mixing in the reactor was provided by a rotating 1000 rpm impeller.
• the pressure in the reactor was maintained to 50 psig and the polymerization temperature was 4°C.
• Example 3 was performed with the Example 1 reagent concentrations, in a 20 minutes minibatch run.

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